Organic compounds containing ether and thio ether linkages



Patented F eb. 8, 1938 \UNITED' STATES ORGANIC COMPOUNDS CONTAINING ETMR AND THIO ETHER LINKAGES Herman A. Bruson, Philadelphia, Pa, assignor to Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application December 24, 11936,

' Serial No. 117,516

11 Claims.

This invention relates to new polyalkylene polyethers containing at least one thio ether link and having the general formula in which A is sulfur or oxygen, R is a cyclic or, substituted cyclic group preferably attached to the atom represented by A through a nuclear carbon atom, a: is one to two and n is two or three. The cyclic group may be aromatic, alicyclic or heterocyclic and may contain substituents such as the alkyl, aralkyl, cycloalkyl, aryl, acyl, alkoxy, nitro, carboxy, and sulfonic groups as well as halogens.

These compounds have properties which render them valuable for use as insecticides; moth-proofing agents, etc. and as intermediates in the preparation of capillary active compounds.

According to the present invention the new polyalkylene polyethers containing at least one sulfur atom in the chain may ,be prepared by reacting an inorganic sulfide, preferably an alkali metal sulfide, with an ether halide of the general formula R-A-(CnH2nO)xCnH-.mY in which R, A, n and a: have the foregoing meanings and Y is a halogen atom. Although all of the halides are operative, the invention will be illustrated by employing the chlorides.

These ether chlorides may be prepared by condensing a dihalogeno ether of the general formula Y-(CnH2nO)x'CnH2nY with an arcmatic, alicyclic or heterocyclic compound which has either a hydroxyl or sulfhydryl group preferably attached to one of its nuclear carbon atoms. The condensation is carried out in the presence of an excess of the dihalogeno ether and sufiicient alkali to unite with only one atom or chlorine. In the case of the phenols and mercaptans the reaction is carried out by dissolving them first in the equivalent amount of aqueous or alcoholic caustic solution and then reacting this solution with the dihalogeno ether. In the case of allcyclic or heterocyclic hydroxy compounds which do not react with alkali hydroxide it is necessary to convert them to the corresponding alcoholate by treatment with metallic sodium or potassium, or with sodium monoxide, before heating with the dihalogeno ether.

Dichloroethers which may be used in the pres plex polyether chlorides are monohydroxy phenols such as phenol, all alkyl phenols including the cresols, xylenols, thymol, butyl, amyl, hexyl, octyl, lauryl and higher alkyl phenols, phenyl, benzyl and cyclohexyl phenols, guaiacol, nitro' phenols, halogenated phenols, alkenyl phenols such as allyl and p-methyl-allyl phenols, hydroxy benzophenone and hydroxy acetophenone etc., salicyclic acid and phenol sulfonic acids as well as the corresponding derivatives of the naphthols and the thio phenols corresponding to the above listed phenols. The operative alcohols are those of the alicyclic series such, for example, as cyclohexanol and its ring substituted products which may be prepared by hydrogenating any of the foregoing phenols, benzyl alcohol, menthol, borneol, etc. The heterocyclic alcohols such as tetrafurfuryl alcohol, Z-hydroxy-benzothiazole and other 2-hydroxy thiazoles and oxazoles may also be used as well as the corresponding mercapto compounds of both the alicyclic and heterocyclic alcohols.

It is thus obvious that the group represented by R in the above formulae may be varied over a wide range of organic radicals and that the atom represented by A may be either oxygen or sulfur irrespective ofthe nature of the group represented by R.

The complex monochloro polyethers prepared from these compounds and a dichioro polyalkylene ether all react readily with an inorganic sulfide, particularly the soluble alkali metal and alkaline earth metal .s'ulfides to form new thio ethers according to the equation This reaction is preferably carried out in an aqueous or alcoholic solution by boiling the mixture of the reactants under a reflux condenser for about four to ten hours, depending on the rate at which any given mixture will react. The

products are crystalline solids or high boiling,-

light-colored liquids. They may be used directly as insecticides, etc. and, when they contain sulfonic acid or other acidic salt forming groups, as wetting, dispersing and emulsifying agents. Those compounds made from the phenols may be sulfonated in either or both of the aromatic rings and the resulting acids or their soluble salts used as emulsifying, wetting, detergent or dispersing agents. The thio ether atoms may also be oxidized to form sulfoxides and sulfones and they may also be treated with alkylating agents to form sulfonlum compounds.

The invention may be illustrated by the. following examples but it is not limited to the exact details of operation, materials used, etc. as it may O-m-csn-o-camm It solidifies to a colorless, crystalline mass. After recrystallization from methanol it has a melting point of 44 C.

Example 2.-A mixture of 82.6 g. of pm-naphthoxy) -;l'-chlorodiethyl ether, g. of sodium sulfide (NazSBHzO), and g. ofetl'lyl alcohol is boiled under a refiux condenser for eight hours and filtered hot. 0n cooling the filtrate solidifies to a waxy mass from which the di(s-naphthoxy' ethoxyethyl) sulfide having the iormulav may be obtained by crystallization irom alcohol. The crystals are colorless needles melting at Example 3.-A mixture consisting of 88.7 g. of p-(p cresyloxy ethoxy) p'-chlorodiethyl ether, 18 g. of sodium sulfide (NazSBHO) and 50 g. of alcohol is boiled under refiux, with agitation, for six hours. The reaction mixture is cooled, fil tered, and the filtrate distilled in vacuo. The product, di(cresyloxy ethoxyethoxyethyl) sulfide, having the formulacomes over at about 295 to 320 C./5 mm. as a colorless oil. Yield 70% of theory.

Example 4.-A mixture consisting of 47 g. of p(2,4-dichlorophenoxy ethoxy) -p'-chlorodiethyl ether, 18 grams of sodium sulfide crystals, and 50 cc. of alcohol is boiled for six hours under a refiux. The product is separated as in Example 3.

It is an oil which distills at 250 to 260 C./5 mm. and has the formula:

Example 5.A mixture consisting of 48 g. of p-tetra-hydroiurfuryloxy-p'-chlorodiethyl ether, 24 g. of sodium sulfide crystals, and 50 cc. oi alcohol wasboiled under reflux for six hours. The filtered reaction mixture was distilled in vacuo. The product comes over about 220 C./'l mm. as a colorless oil. It is di(tetrahydromriuryloxy ethoxyethyl) sulfide having the formula- Example 6.A mixture consisting 01 20 g. 01' flake sodium sulfide (60% purity), 100 g. of alcohol, and 62.6 g. of p-(p-a, a, 'y-tetramethyl butylphenoxy) -p-chlorodiethyl ether .was boiled under reflux for eight hours. The reaction prod- 2,1ov,sos 1 uct was poured into water, the oily layer'taken up in benzene, separated, washed, and distilled in vacuo. The product distills with a little decomposition at about 320 C./3 mm. as a pale yellow oil. It is di(p-u, a, 'y-tetramethyl butylphenoxy ethoxyethyl) sulfide having the formula- Example 7.A mixture consisting of 60 g. of sodium sulfide (NazBBHzO), 100 cc. of alcohol, and 122 g. of p-phenoxyethoxy-p'chlorodiethyl ether was-boiled under reflux for seven hours. It was then filtered and the filtrate distilled in vacuo. The product, di(phenoxyethoxyethoxyethyl) sulfide, having the formula (Go-mm-o-caw-o-cmQs cm (cnr-oOoonr-cn-o-cn-cm s (5H; (EH: 41H; is a pale yellow, viscous oil.

Example 9.A mixture consisting of 30 g. of sodium sulfide (-NaaS.9HzO), 70.6 g. of p-p-cyclohexylphenoxy-p-chlorodiethyl ether, and 50 cc. of alcohol is boiled under refiux for fourhours and filtered hot. The reaction product, di(pcyclohexylphenoxy ethoxyethyl) sulfide, having the formulacrystallizes out on' cooling. It can be recrystallized from alcohol, and forms colorless crystals melting at 66 C.,

Example 10.A mixture consisting of 67 g. of p-p-benzylphenoxy-p'-chlorodiethyl ether, 24 g. of sodium sulfide (NazSilmO), and 50 g. of alcohol is boiled for seven hours under reflux, and worked up as in Example '7. The product is an oil which boils above 360 'C./1 mm. It is di(pbenzylphenoxy ethoxyethyl) sulfide having the formula Example 11.A mixture consisting oi! 64 g. of p-p-phenylphenoxy-fl-chlorodiethyl ether, 24 g. of sodium sulfide (NazS.9I-Iz0) and 50 cc. of alcohol is boiled five hours under reflux. The oil obtained crystallizes on cooling to colorless crystals which, upon crystallization from alcohol, melt at 68 C. The product, di(p-phenyi-phenoxy ethoxyethyl) sulfide has the formula Example 12.A mixture of 55 g. of thiophenol, 286 g. of p, p'-dichlorodiethyl ether, 23.4 g. oi sodium hydroxide, and 25 cc. of water was heated at to C. under refiux, with stirring, for six hours. The water was then distilled oil, the sodium chloride removed by filtration, and the filtrate fractionated in vacuo. The phenyl-thioethoxyethyl chloride having the formula CeH5S-C2H4OCH2CH2C1 was obtained as a colorless oil boiling at 141 to 157 C./4 mm., yield 96%.

A mixture of 21.6 grams ofv the phenyl-thioethoxyethyl chloride, 12 g. of sodium sulfide (NazS.9H2O) and 25 cc. of alcohol was boiled under reflux six hours. The oil formed was separated, washed with water, and distilled in vacuo.

The di(phenyl-thioethoxyethyl) sulfide having the formula came over at 275 to 283 C./4 mm. as an oil.

Example 13.A mixture consisting of 1 mol. equivalent mercaptobenzothiazole, 1.2 mols of sodium hydroxide in an equal weight of water, and 3 mols of 3, 5'-dichlorodiethyl ether was heated at C. for eight hours under reflux, with constant stirring. The product obtained, namely: benzothiazyl-thioethoxy-ethyl chloride, having the formula C-S-CzHt-O-CHz-CHzCl f.

formed a yellow oil boiling at to 200 C./ 3 mm.

A mixture of 27.3 g. of the benzothiazyl-thioethoxyethyl chloride, 12 g. of sodium sulfide (NazSflHzO), and 25 g. of alcohol was boiled under reflux for five hours, with stirring. The oil, upon fractionation in vacuo, yielded the desired product as a yellow oil, boiling at 290 to 300 C./4 mm. It is di(benzothiazyl-thioethoxyethyl) sulfide having the formula Yield78%.

In the above examples the sodium sulfide can be replaced by a molecularly equivalent of potassium sulfide or other water-soluble inorganic sulfide.

I claim:

2. A .compound having the general formula in which R is an aromatic hydrocarbon radical attached to the oxygen atom by means of a nuclear carbon atom. V

3. A compound having the general formula- (RO--C2H4- -OC2H4) as in which R is an aromatic radical attached to the oxygen atom by means of a nuclear carbon'atom.

4. A compound having the general formula in which R is an aromatic radical and A is a member of the group consisting of oxygen and sulfur, the radical represented by R being attached to the atom represented by A by means of a nuclear carbon atom.

5. A compound having the general formula in which R is an organic cyclic group selected from the group consisting of aromatic, alicyclic and heterocyclic radicals, A is a member of the group consisting of oxygen and sulfur, a: is one to two and n is two to three, the radical represented by R being attached to the atom represented by A by means of a nuclear carbon atom.

6. The process of preparing di(phenoxy ethoxyethyl) sulfide which comprises heating a mixture of sodium sulfide and p-phenoxy-p'whlorodiethyl ether in an inert solvent.

7. The process of preparing compounds of the general formula (R-OC2H4OC2H4)2S in which R is an aromatic radical attached to the oxygen atom by means of a nuclear carbon atom which comprises heating an alkali metal sulfide and an ether chloride having the general formula in an inert solvent.

8. The process of preparing compounds of the general formula (R-A-C2H4-OC2H4) as in which R is an aromatic radical and A is a member of the group consisting of oxygen and sulfur, the radical represented by R being attached to the atom represented by A by means of a nuclear carbon atom, which comprises heating an ether chloride of the general formula with an alkali metal sulfide in an inert solvent.

9. The process of preparing compounds of the in which R is an organic cyclic group selected from the group consisting of aromatic, alicyclic and heterocyclic radicals, A is a member of the group consisting of oxygen and sulfur, the radical represented by R being attached to the atom represented by A by means of a nuclear carbon atom, a: is one to two and n is two to three which consists in heating an ether halide of the general formula halogen with an alkali metal sulfide.

10. Di- (p-naphthoxyethoxyethyl) sulfide having the formula- OC3HiO-C2H4 11. Di- (p-phenylphenpxyethoxyethyl) sulfide, having the formula-- HERMAN A. BRUSON. 

